US4543189A - Removal of complexed zinc-cyanide from wastewater - Google Patents
Removal of complexed zinc-cyanide from wastewater Download PDFInfo
- Publication number
- US4543189A US4543189A US06/620,363 US62036384A US4543189A US 4543189 A US4543189 A US 4543189A US 62036384 A US62036384 A US 62036384A US 4543189 A US4543189 A US 4543189A
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- Prior art keywords
- zinc
- soluble
- reactor
- sup
- cyanide
- Prior art date
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- 239000002351 wastewater Substances 0.000 title claims abstract description 20
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000010802 sludge Substances 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 50
- 229910052725 zinc Inorganic materials 0.000 claims description 50
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 7
- 229960003351 prussian blue Drugs 0.000 claims description 7
- 239000013225 prussian blue Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 6
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 6
- 229940007718 zinc hydroxide Drugs 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- -1 ferrous chlorides Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/903—Nitrogenous
- Y10S210/904—-CN containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/911—Cumulative poison
- Y10S210/912—Heavy metal
Definitions
- This invention is directed to a method for treating wastewater, such as blast furnace blowdown water, for removal of zinc and cyanide.
- blast furnace blowdown water is utilized to cool and cleanse gases coming out of the furnace. Such water is generally recycled, but a certain portion of this water is removed from the system for discharge into the environment. Such discharge water contains soluble zinc and cyanide which are objectionable. Such discharge water containing soluble zinc and free cyanide is referred to herein as blast furnace blowdown.
- cyanide which is soluble and available to react with zinc is referred to herein as free cyanide.
- Total soluble cyanide includes free cyanide (as defined herein) plus a soluble ferrocyanide and/or a soluble ferricyanide which, unlike free cyanide, are not available to react with zinc. Free cyanide will react with soluble zinc to form a zinc-cyanide complex, which is an environmentally harmful complex that is not removed from solution by traditional pH adjustment of the water.
- One method for removing soluble zinc from acid steel plant wastewater consists of treating wastewater with a mixture of alkali-water slurry and recycled sludge formed later in the method. This mix neutralizes the acidity of the wastewater and precipitates a substantial portion of the zinc value as solids which settle out as a sludge, a portion of which is recycled as described above.
- Such process is described in commonly assigned U.S. patent application Ser. No. 291,439 filed Aug. 10, 1981, by Stewart T. Herman et al.
- the process described therein is referred to as a high density sludge process. Unfortunately, this process is not effective for treating zinc-cyanide complexes.
- a method for removing cyanide which has been complexed with zinc in a wastewater is disclosed in U.S. Pat. No. 4,312,760 issued Jan. 26, 1982 to Roy G. Neville.
- the method disclosed therein requires the addition of ferrous sulfate in the presence of bisulfite ions.
- Neville discloses using a ferrous ion concentration of 200 to 300 ppm.
- Neville also requires the presence of bisulfite ions and the presence of an oil layer on top of the water to be treated to avoid oxidation of ferrous ion to ferric ion. Ferric ion will not react with complexed zinc-cyanide. It is, therefore, desirable to develop a process which does not require the expense and added step of bisulfite addition and an oil covering.
- the invention can lower soluble zinc and free cyanide levels of blast furnace blowdown without the disadvantages of the prior art.
- the invention includes a multiple stage process wherein the first stage includes addition of ferrous ions to a critical minimum concentration of 250 to 400 ppm, while the pH of the water is held below 7.0 by means of addition of a mineral acid, e.g. sulfuric or hydrochloric acid. Such acid may already be present with the source of ferrous iron as in the case of waste pickling liquors from steel mills.
- a mineral acid e.g. sulfuric or hydrochloric acid
- the wastewater in a second reactor next has its pH adjusted to between 9.5 to 10.0 to cause zinc to precipitate as zinc hydroxide and to cause the cyanide to precipitate as prussian blue.
- sludge from a settling tank is recycled to a third reactor and mixed with an alkaline material, whereupon the mixture is processed back to the second reactor, such that the amount of dry solids recycled per unit time is equal to between 20 and 100 times the amount precipitated per unit time in the second reactor, and the pH is controlled to between 8.8 and 9.4.
- the wastewater is stirred to prevent settling of precipitates. Thereafter, the wastewater is sent to a settling tank from which clean effluent overflows, and the sludge is sent to landfill, with a small portion recycled as described above.
- FIG. 1 is a graphical depiction of the unexpected relationship between free cyanide concentration (ppm) and ferrous ion concentration (ppm) in blast furnace blowdown.
- FIG. 2 is a graphical depiction of the unexpected relationship between free cyanide concentration (ppm) and ferrous ion concentration (ppm) for starting cyanide concentrations of 6, 15 and 30 ppm in blast furnace blowdown.
- FIG. 3 is a graphical depiction of the unexpected relationship between soluble zinc concentration and free cyanide concentration in blast furnace blowdown.
- FIG. 4 is a diagrammatic flow sheet showing the invention without sludge recycling.
- FIG. 5 is a diagrammatic flow sheet showing the invention having sludge recycling.
- FIG. 1 shows the unexpected relationship between free cyanide (defined herein as cyanide available to react with soluble zinc) and the concentration of ferrous ion in a mixture of ferrous ions and blast furnace blowdown.
- free cyanide defined herein as cyanide available to react with soluble zinc
- concentration of ferrous ion in a mixture of ferrous ions and blast furnace blowdown As the curve in FIG. 1 suggests, free cyanide decreases to an unexpected low plateau (between 1-2 ppm) when ferrous ion concentration is in the range of 250 to 400 ppm.
- Such relationship was experimentally observed in blast furnace blowdown waters having a cyanide inlet concentration over a range of 6 ppm (curve A), 15 ppm (curve B) and 30 ppm (curve C) as shown in FIG. 2.
- FIG. 4 discloses a flow diagram of a process of the invention. Incoming blast furnace blowdown to be treated is processed to a first reactor 1.
- the term "processed” includes flow by gravity or movement by means of suitable pumping and valving devices.
- Sufficient soluble ferrous ion in the form of aqueous ferrous sulfate, aqueous ferrous chloride or other aqueous soluble ferrous salts is added to provide a concentration of ferrous ion of at least 250 to 400 ppm. It is important that the pH in reactor 1 be maintained below 7 in order to keep all the ferrous ions in solution and available to break the zinc-cyanide complex.
- the pH is controlled by means of the addition of a mineral acid, e.g. sulfuric or hydrochloric acid. Such acid may already be present with the source of ferrous ion as in the case of waste pickling liquors from steel mills.
- zinc-cyanide complex is converted to free zinc ion (which can be precipitated at a later stage by pH control as described below) plus soluble ferrocyanide which precipitates as prussian blue in the presence of excess ferrous ion at a later stage by pH control.
- the mixture is processed as overflow from first reactor 1 to a second reactor 3, where pH is adjusted to between 9.5 and 10.0 by means of addition of an alkaline material, e.g., aqueous lime, sodium hydroxide or sodium carbonate.
- an alkaline material e.g., aqueous lime, sodium hydroxide or sodium carbonate.
- the pH control is accomplished automatically by conventional pH measuring and controlling device 4.
- reactors 1 and 3 are continuously stirred by conventional stirring devices (not shown), in order to keep solids suspended therein.
- reactor 3 The contents of reactor 3 are next processed to settling basin 5, to permit the solid matter (zinc hydroxide, prussian blue and ferrous hydroxide) to settle out.
- Overflow from settling basin 5 now only contains soluble zinc in an amount less than 0.45 ppm, and a soluble cyanide in an amount of less than 3 ppm. Such overflow can now be discharged, or sent to further treatment to remove solids, if necessary in order to meet the standards for total zinc and/or cyanide.
- the precipitates being settled in settling basin 5 settle out slowly, and in order to enhance this settling process, the effluent can also be passed to a conventional filter process (not shown) in order to lower the total suspended solids, and thereby lower total zinc and total cyanide content before such effluent is discharged. Sludge underflow can be removed from settling basin 5 for dumping.
- overflow mixture is processed into second reactor 3, where it combines with overflow from first reactor 1.
- pH is preferably kept at about 8.8 and 9.4 for optimum zinc removal.
- Wastewater having soluble zinc in the range of 10 to 75 ppm and free cyanide in the range of 6 to 30 ppm were processed in a continuous process at a flow rate of 125 ml/min to a first reactor where aqueous ferrous sulfate was added at a rate of 10 ml/min to maintain ferrous ion concentration of 300 ppm in the first reactor.
- the pH was maintained at or below 7.0 by addition of sulfuric acid to the aqueous ferrous sulfate.
- Residence time of material in reactor 1 was 1 to 2 minutes, with overflow being processed to a second reactor, where pH was maintained at between 8.8 and 9.2 and where a portion of recycled sludge was added at the rate of approximately 20 to 50 times the amount of solids precipitated per unit time in reactor 1, after the sludge had been previously mixed in a third reactor with sufficient lime to maintain the appropriate pH in the second reactor. Residence time in the second reactor was approximately 5 minutes.
- the pH measuring and controlling device was a Leeds and Northrup Speedomax W Recorder.
- the contents of the second reactor were processed to a settling basin, where solids settled out, providing an effluent for discharge and a sludge for recycling and discharge.
- Such treatment resulted in an effluent having a soluble free cyanide concentration of less than 2 ppm, and a soluble zinc concentration of between 0.10 and 0.30 ppm, with a total soluble cyanide concentration of less than 3 ppm.
Abstract
Description
3Zn(CN).sub.4.sup.-2 +2Fe.sup.+2 →3Zn.sup.+2 +2Fe(CN).sub.6.sup.-4
Zn.sup.+2 +2OH.sup.- →Zn(OH).sub.2 ↓
Fe(CN).sub.6.sup.-4 +2Fe.sup.+2 →Fe.sub.2 Fe(CN).sub.6 ↓
Fe.sup.+2 +2OH.sup.- →Fe(OH).sub.2 ↓
Claims (6)
3Zn(CN).sub.4.sup.-2 +2Fe.sup.+2 →3Zn.sup.+2 +2Fe(CN).sub.6.sup.-4.
Zn.sup.+2 +2OH.sup.- →Zn(OH).sub.2 ↓
Fe(CN).sub.6.sup.-4 +2Fe.sup.+2 →Fe.sub.2 Fe(CN).sub.6 ↓
Fe.sup.+2 +2OH.sup.- →Fe(OH).sub.2
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/620,363 US4543189A (en) | 1984-06-13 | 1984-06-13 | Removal of complexed zinc-cyanide from wastewater |
US06/748,660 US4606829A (en) | 1984-06-13 | 1985-06-25 | Removal of complexed zinc-cyanide from wastewater with improved sludge stability |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/620,363 US4543189A (en) | 1984-06-13 | 1984-06-13 | Removal of complexed zinc-cyanide from wastewater |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/748,660 Continuation-In-Part US4606829A (en) | 1984-06-13 | 1985-06-25 | Removal of complexed zinc-cyanide from wastewater with improved sludge stability |
Publications (1)
Publication Number | Publication Date |
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US4543189A true US4543189A (en) | 1985-09-24 |
Family
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Family Applications (1)
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US06/620,363 Expired - Lifetime US4543189A (en) | 1984-06-13 | 1984-06-13 | Removal of complexed zinc-cyanide from wastewater |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4606829A (en) * | 1984-06-13 | 1986-08-19 | Bethlehem Steel Corporation | Removal of complexed zinc-cyanide from wastewater with improved sludge stability |
US4802995A (en) * | 1987-06-05 | 1989-02-07 | Rostoker, Inc. | Method for decomposing the cyanide radical in cyanide-bearing wastes or materials |
US4895659A (en) * | 1987-04-30 | 1990-01-23 | Regents Of The University Of Minnesota | Method for metal and cyanide recovery from plating baths and rinse waters |
US5427691A (en) * | 1992-12-02 | 1995-06-27 | Noranda, Inc. | Lime neutralization process for treating acidic waters |
US5443622A (en) * | 1994-02-28 | 1995-08-22 | Kennecott Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
US5616168A (en) * | 1994-02-28 | 1997-04-01 | Kennecott Utah Copper Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
US5618439A (en) * | 1993-04-20 | 1997-04-08 | Boliden Contech Ab | Method for purifying industrial sewage water |
US5647996A (en) * | 1995-06-16 | 1997-07-15 | Ormet Corporation | Groundwater total cyanide treatment method |
WO2000009452A1 (en) * | 1998-08-13 | 2000-02-24 | Fuji Hunt Photographic Chemicals, Inc. | A process for removing silver in the presence of iron from waste effluent |
US6139753A (en) * | 1997-03-21 | 2000-10-31 | Geo2 Limited | Method for treating acidic waste water |
US6409927B1 (en) * | 1998-06-03 | 2002-06-25 | Enrique-Ruben Cardenas-Granguillhome | Process for the treatment of polluted metal-mechanic industrial wastewater and urban water |
WO2023098190A1 (en) * | 2021-12-01 | 2023-06-08 | 湖南邦普循环科技有限公司 | Treatment method for wastewater containing cyanide and oxalate |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3575853A (en) * | 1968-12-24 | 1971-04-20 | Lab Betz Inc | Waste water treatment |
US3738932A (en) * | 1971-04-19 | 1973-06-12 | Bethlehem Steel Corp | Method for treating acid water containing metallic values |
US3931007A (en) * | 1972-12-19 | 1976-01-06 | Nippon Electric Company Limited | Method of extracting heavy metals from industrial waste waters |
US4169053A (en) * | 1975-08-08 | 1979-09-25 | Nippon Electric Co., Ltd. | Method of treating waste waters containing solid-phase difficultly-soluble compounds |
US4211646A (en) * | 1977-10-31 | 1980-07-08 | Texaco Inc. | Waste water process |
US4312760A (en) * | 1980-02-19 | 1982-01-26 | Neville Roy G | Method for the removal of free and complex cyanides from water |
US4465597A (en) * | 1981-08-10 | 1984-08-14 | Bethlehem Steel Corp. | Treatment of industrial wastewaters |
-
1984
- 1984-06-13 US US06/620,363 patent/US4543189A/en not_active Expired - Lifetime
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3575853A (en) * | 1968-12-24 | 1971-04-20 | Lab Betz Inc | Waste water treatment |
US3738932A (en) * | 1971-04-19 | 1973-06-12 | Bethlehem Steel Corp | Method for treating acid water containing metallic values |
US3931007A (en) * | 1972-12-19 | 1976-01-06 | Nippon Electric Company Limited | Method of extracting heavy metals from industrial waste waters |
US4169053A (en) * | 1975-08-08 | 1979-09-25 | Nippon Electric Co., Ltd. | Method of treating waste waters containing solid-phase difficultly-soluble compounds |
US4211646A (en) * | 1977-10-31 | 1980-07-08 | Texaco Inc. | Waste water process |
US4312760A (en) * | 1980-02-19 | 1982-01-26 | Neville Roy G | Method for the removal of free and complex cyanides from water |
US4465597A (en) * | 1981-08-10 | 1984-08-14 | Bethlehem Steel Corp. | Treatment of industrial wastewaters |
US4465597B1 (en) * | 1981-08-10 | 1994-04-25 | Tetra Tech | Treatment of industrial wastewaters. |
US4465597B2 (en) * | 1981-08-10 | 1997-07-01 | Tetra Tech | Treatment of industrial wastewaters |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4606829A (en) * | 1984-06-13 | 1986-08-19 | Bethlehem Steel Corporation | Removal of complexed zinc-cyanide from wastewater with improved sludge stability |
US4895659A (en) * | 1987-04-30 | 1990-01-23 | Regents Of The University Of Minnesota | Method for metal and cyanide recovery from plating baths and rinse waters |
US4802995A (en) * | 1987-06-05 | 1989-02-07 | Rostoker, Inc. | Method for decomposing the cyanide radical in cyanide-bearing wastes or materials |
US5427691A (en) * | 1992-12-02 | 1995-06-27 | Noranda, Inc. | Lime neutralization process for treating acidic waters |
US5618439A (en) * | 1993-04-20 | 1997-04-08 | Boliden Contech Ab | Method for purifying industrial sewage water |
US5616168A (en) * | 1994-02-28 | 1997-04-01 | Kennecott Utah Copper Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
US5443622A (en) * | 1994-02-28 | 1995-08-22 | Kennecott Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
US5647996A (en) * | 1995-06-16 | 1997-07-15 | Ormet Corporation | Groundwater total cyanide treatment method |
US5853573A (en) * | 1995-06-16 | 1998-12-29 | Ormet Corporation | Groundwater total cyanide treatment apparatus |
US6139753A (en) * | 1997-03-21 | 2000-10-31 | Geo2 Limited | Method for treating acidic waste water |
US6409927B1 (en) * | 1998-06-03 | 2002-06-25 | Enrique-Ruben Cardenas-Granguillhome | Process for the treatment of polluted metal-mechanic industrial wastewater and urban water |
WO2000009452A1 (en) * | 1998-08-13 | 2000-02-24 | Fuji Hunt Photographic Chemicals, Inc. | A process for removing silver in the presence of iron from waste effluent |
US6126840A (en) * | 1998-08-13 | 2000-10-03 | Fuji Hunt Photographic Chemicals, Inc. | Process for removing silver in the presence of iron from waste effluent |
WO2023098190A1 (en) * | 2021-12-01 | 2023-06-08 | 湖南邦普循环科技有限公司 | Treatment method for wastewater containing cyanide and oxalate |
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